Azodyestuffs containing a



AZODYESTUFFS CONTAINING A fl-CHLORO- CROTONYL RADICAL Werner Bossard,Riehen, near Base], and Herbert Seiler, Basel, Switzerland, Paul Dussy,St.-Lonis, France, Marcel Reding and Andr Pugin, Riehen, near Basel, andHans Peter Kiillilrer, Munchenstein, Basel-Land, Switzerland, assignorsto J. R. Geigy A.-G., Basel, Switzerland No Drawing. Filed Oct. 16,1959, Ser. No. 846,800 Claims priority, application Switzerland Oct. 21,1958 i 5 Claims. (Cl. 260-151) The present invention relates to reactivedyes, which can be fixed on textile fbres, containing recurringcondensable groups such as hydroxy and amino groups, e.g. on natural orregenerated cellulose and on keratinous fibres, such as wool. Anotherfeature of the instant invention is to provide processes for themanufacture of the new dyes. The invention also relates to dyed materialof exceptional wet-fastness, primarily to dyed cellulose material,produced with the new dyes.

The new dyes of our invention correspond to the general Formula I:

. XnD(N- OCH=C-Z) H-( )q-l In this formula, X means the same ordifferent acid dissociating, watersoluble alkali metal and ammoniumsalt-forming groups, e.g. carboxylic acid, phosphonic acid, acylatedsulphonic acid amide, disulphimide and preferably sulphonic acid groups,

It Means a lower whole number of at least two, preferably 2 to D meansthe radical of monoazo dyestufi,

D, more precisely, is monoazo dye selected from the groups consisting ofbenzene-azo-benzene dyes, of benzene-azo-naphthalene dyes, ofbenzene-azo-pyrazole dyes, and of naphthalene-azo-naphthalene dyes,which monoazo dyes contain each of the substituents X and N-o 0-0 H=C H()o-l Y at the phenyl radical in p-position to the azo group;

(b) 4-(phenyl-azo)-5-pyrazolone dyes containing at the phenyl radical asulphonic acid group in o-position to the azo-group and a -N-C 0-0 H=CH-( -1 Y substituent in meta-position to the azo group;

(0) 1-(phenyl-azo)-2-aminonaphthyl dyes containing at the phenyl radicala sulphonic acid group in oposition to the azo group and a substituentin one of the positions meta and para to the azo group;

(d) 2-(phenyl-azo)-1-hydroxynaphthyl dyes containing a sulphonic acidgroup at the phenyl radical in 0-- position to the azo group and a Z-N--C 0-0 H=O II-( -1 Y -N--C OCH=C q-l Y substituent at the azo-freering of the naphthyl radical and containing also one of the metalscopper, chromiumand cobalt in complex union;

(f) 0.0'-Dihydroxy-naphthyl-azo-naphthyl dyes containing a -N-C 0-0 H=CH-( )q--1 Y substituent at the azo-free ring of one of the naphthylradicals and containing also one of the metals copper, chromium andcobalt in complex union.

R in Formula I is a two-valent lower aliphatic radical such asmethylene, ethylene, propylene, butylene, hydroxyethylene,hydroxypropylene,

Y in Formula I is a halogen of the atomic number 17 to 35, andpreferably is chlorine,

Z in Formula I is lower alkyl, preferably methyl, and

m and q each are one of the integers one and two.

The dyes of the instant invention are obtained by densing a dye of thegeneral Formula H:

wherein X, D, R, n, m and q have the same meanings as given in Formula Iand as explained above, with a carboxylic acid halide of the FormulaIII:

Y-C O--CH=CZ (III) An alternative method of producing the dyes of theinstant invention consists in using dyestuff components containingtogether at least one Metal containing monoand disazo dyes of ourinvention preferably are of the one basic dye to one metal type if theheavy metal is copper and of the two basic dye to one metal type if theheavy metal is cobalt or chromium;

Patented Mar, 24, race a 3 in the latter case, two same or differentbasic dyes may be coordinated with chromium or cobalt.

The dyestuffs according to the present invention are easilywatch-soluble and, in contrast to comparable dyestuffs which contain achloracetylamino or a p-chloroor a fl-bromo-propionylamino group insteadof the acylamino group according to the invention, are particularlysuitable for the preparation of wet-fast dyeings on cellulose fibers byimpregnating them with dyestufr' solutions andsubsequent alkalinefixation in the warm.

It is well known in the art of dyeing that it is indispensable forattaining outstanding wet-fastness properties of cellulose dyeingsproduced with reactive dyes to thoroughly wash out any unfixed dyestuff.Owing to this washing process considerable loss in depth of shade mayoccur. It is an advantage of our dyes that they show minimal loss indepth of shade on washing after the fixation on the fibres.

The following examples illustrate the invention.- The specific manner ofapplication of the new dyestuffs described in each of the examples isvalid mutatis mutandis for each dyestulf of the invention. In theexamples, if not stated otherwise, parts are given as parts by weightand their relationship to parts by volume is as that of grammes to cubiccentimetres. The temperatures are in degrees centigrade.

EXAMPLE 1 42.1 parts of the aminoazo dyestuff 4 traced in a small sampleby diazotisation and coupling, the dyestutf of the formula SOsH SOJII isprecipitated by the addition of sodium chloride, filtered off and washedwith diluted sodium chloride solution. After drying in the vacuum, thedyestuti is an orange coloured powder which dissolves in water with ayelloworange and in concentrated sulphuric acid with an orangeredcolour.

2 parts of the dyestutf obtained above are dissolved in a dye bath in4000 parts of water. 100 parts of cotton are entered at -45 the bath isheated within 30 minutes to 80, g. of sodium chloride per litre beingadded in portions. At the end of this time, 20 g. of trisodium phosphateper litre are added and the goods are treated for another minutes atthis temperature. Finally, the goods are rinsed and soaped at the boilfor 30 minutes during which process the soaping solution is onlycoloured a little. A clear, level, yellow dyeing is obtained which isfast to light, washing and boiling.

If in paragraph 1 of the above example, instead of 42.1 parts of thedyestuff named, equimolecular parts of the dyestuffs given in thefollowing Table 1 are used and the condensation is performed undercorresponding conditions with a small excess of the fi-chloralkenecarboxylic 50,13 acid chloride given in column 3 of the table, thendyestuffs l are obtained which produce cellulose dyeings havingsimilarly good wet fastness properties if the dyeing process 3 describedabove is used. The ammoazo dyestuffs given in Table 1 are obtained bydiazotising the corresponding amino compound and ,1 then coupling withthe corresponding aminobenzene derivatives to form the p'amino monoorp-amino dis-azo 40 dyestutf at a pH value of 2.0 to 4.5.

Table 1 No. Aminoazo dycstull Condensing agent :lhade on atton2-amlnonaphthalene-4.8-dhulphonic acid)1-amlno-2- methoxy-5-mcthylbenzene fl-chlgrohcrotoilc yellow aci c lori e.1-amlnonuphthalone-4.6-disl1lpl1onie ncitl-)l-arulno-3methylbenZeno dDo. 2ominonephthulene-4.S-disnlphonle acld- 1-N-ethylamlno13 methylbcnmne- D0. z-omlnonophthnlene-t.8-disulphonic acid)l-aminoJ-ucctylamlnobenu-ne. Do. 241minonaphthalene-5.7-dtsulphonicacld-)l-amino-2-meth0xyben1,ene D0. l-aminonophthaleno-4.t)-disulphonicacid )I-amino-2-methoxy-5-methyl-hcnz no. Do. l-aminobon1cue-2.5-disulhonlc acld l-(3-arninophenyl) 3-methyl fi pyruzolonm Do.2-urnlnonaphthalene-4.R isulpllonic acld-- 1-amin0hcnzene Do.2-umlnonuphtlialeno-B.8-dtsulphonic actd l-amtno-3-methoxyhcmrne Do.l-hydroxy-4-aminobenzcnc6-carboxyllc acid-G-sulphontc aeid-1-amino-2-mcthoxybcn- Do.

zone. fi-mcthyl-QJW-sulphot-arninophenyl)-bcnzthiazole-7-sulphonlc acldl-nmlnobenzcne do Do. mixture from 3-aminopyrenc-fifldisulphonlc acidand 3-amlnophyrenc-5.lO-dlsulpltonio do yellowacld--l-tnnln0-3-methylbenzene. orange.

are dissolved with sodium carbonate in 500 parts of water so that thereaction is neutral. 21 parts of fi-chlorocrotonic acid chloride in 100parts of acetone and an aqueous sodium carbonate solution are so addeddropwise simultaneously to this solution over a period of 1 hour at30-35 that the mixture always has a neutral reaction. As soon as no morefree amino groups can be EXAMPLE 2 18.8 parts ofl.3-diaminobenzene-4sulphonic acid are dissolved with the addition ofsodium carbonate at a pH value of 6.5-7 in 200 parts of water. 21 partsof 13-chlorocrotonic acid chloride in 50 parts of acetone are addeddropwise simultaneously with an aqueous sodium carbonate solution atl0-l5 within 1 hour in such a manner that the reaction always remainsneutral. On completion of the condensation, the reaction product isprecipitated by the addition of sodium chloride, filtered oif, dissolvedin 400 parts of water and diazotised at with 25 parts of 30%hydrochloric acid and 6.9 parts of sodium nitrite. The diazoniumcompound formed is coupled at a pH of 44.5 with a solution of 23.9 partsof 2-amino'8-hydroxynaphthalene-G-sulphouic acid in 200 parts of water.Oncompletion of the coupling, the new dyestuif of the formula S'OsH HON=N 1 H0 is is precipitated with sodium chloride, filtered off and driedin the vacuum at 4045. It is a dark red powder which dissolves in waterwith a red and in concentrated sulphuric acid with a scarlet colour.

If cotton is impregnated in a foulard with a 1% solution of thisdyestuff, with the addition of 20 g. of sodium carbonate per'litre, at50", then rolled up, heated for 2 hours at 95, rinsed and soaped at theboil for 30 minutes, in which process only a little dyestuif is washedaway, then a brilliant red dyeing is obtained which is fast to light andboiling.

Dyestuffs having similar properties are obtained if the diaminobenzenesulphonic acids given in the following Table 2 are condensed with theB-halogen alkene carboxylic acid chlorides given in column 3 under thetest conditions described in the above example and the condensationproduct is diazotised and coupled with equivalent parts of the couplingcomponents given in column 5 at the pH values given in column 4.

6 (obtained by coupling diazotisedZ-amino-l-hydroxybenzene-4.6-disulphonic acid with 2amino5-hydroxy-'naphthalene-7-sulphonic acid in an alkaline medium and treating theaminomonoazo dyestuif obtained with agents giving off copper) aredissolved, with a neutral reaction, with sodium carbonate in 1200 partsof water. 21 parts of fl-chlorocrotonic acid chloride in parts ofacetone and an aqueous sodium carbonate solution are added dropwisesimultaneously to this solution within 1 hour at 30-35 in such a mannerthat the reaction mixture always remains neutral. As soon as no moreaminomonoazo dyestufi can be traced by diazotising and cou- I pling asmall sample, the new dyestufi of the formula HOaS OC O I 80311 H038 NHOCCH=C--CH ing. A strong, ruby dyeing is obtained which is fast to lightand boiling.

Dyestuifs having similar properties are obtained if,

instead of the above aminomonoazo dyestuif, corresponding parts of thecomplex metal compounds of the aminoazo dyestuffs given in the followingTable 3 are used and the condensation is performed under the samereaction conditions with the corresponding number of parts of B-halogenalkene carboxylic acid chloride.

Table 2 No. Diamino com- Condensing agent Coupling Coupling componentShade on pound at pH cotton 1 1.3-diamino-benfl chlorocrotonic 7-8i-benzoylarnino-shydroxy-naphthalene-3.tlrdisuiphonlc red.

zene-4-suiacid chloride. acid. phonic acid. 2 do -do 6-7 1-(2chloro fisulpho-phenyl)-3-methyl-5-p azolone. yellow.

6-7 l-(2'igaphthyl)-3methyl-5-pyrazolone-5'.7 -disulphonic D0.

ac 6-7 1-(2.5-dlchloro-4'-sulphophenyl)-3-met'nyl-5-pyrazolone Do. 4-5i-(3'-sulphoghenyl)-3-me"h I-B-iminopyrazole Do. 4-5 2-nminonapthalene-Mu onic acid orange. i -5 2-aminonaphthslene-5.7-t.iiaulphonicacid. Do. 4-5 2-aminonaphthalenc-Bddisulphonic acid Do. 4-5 Z-N-Xnwthylamin0-841ydroxynaphthalene-tlsuiphonic blue ac rc 7-82-(fl-chlorocrotonylamino)-5-hydroxyuaphthalenc-7- orange.

sul honlc acid. 11 1.3-dlamino-ben- B'cnlorocrotordc 7-8 l-(fi-clorocrotonylamlno)-8-hydroxynaphthalene-3.6- red.

.-|.ene-4s acid chloride. disulphonic acid.

phonic acid.

do 8-8. 5 Z-hydroxynaphthnlene-3.6- lisulphonic ncid. do 8-8. 52-l1ydroxynaphthalene-tm'disulphonic acid lA-difi lgilllfi-bfin- 4-4. 5Z-amino-SFhydroxynsplithaienecsulphonic acid zenes phonic acid. 15 do do44.5 Z-aminonaphthaiene-BJ-disuiphonie acid orange. 16 do 4'452-aminonaphthslene-3.6-disu.lphonic acid Do.

EXAMPLE 3 The aminoazo dyestuffs given in Table 3 are produced 58 partsof the aminomonoazo dyestutf of the formula by f i i with HO S 0 sodiummtnte in mineral acid solution and coupling the diazo compound with thecorresponding coupling component in a pyridine-soda alkaline or in apyridine-ammonia alkaline medium. The amino-o,o'-dihydroxyazo compoundsobtained are metallised by treating in the known manner with the usualagents giving off heavy metal.

Table 3 Aminoazo dyestuil Heavy metal complex Shade on Condensing agentcotton 1-omin0-2-l1ydroxybenzene'esulphonic ncl(l- 2-nmlno5 hydroxyuahthaiene-I-sulphonie acid.

l-nznino-Z-hy roxybenzeuo esulphonic acid--1-omino-&

hydroxynnphthaleneALG-disulphonlc acid.

l-nmino-2-hydroxyhenzene-5-su] phonic ncid-*1-an1lno-8- hyddroynaphthalone-3.6-disulphonic acid.

raisin.

violet.

fl chlorocrotonic acild chloride.

EXAMPLE 4 59 parts of the sodium salt of the chromium-containing monoazo dyestufi of the type 2 dyestuif molecules to 1 chromium atom(obtained by coupling equimolecular amounts ofl-diazo-2-hydroxy-6-nitronaphthalene-Lsulphonic acid with 2amino-5-hydroxynaphthalene-7-sulphonic acid in an alkaline medium andreacting in the warm with a 0.6 molar amount of the sodium salt ofdisalicylato chromic acid), are dissolved in 300 parts of water with aneutral reaction. At 0-S, 21 parts of f3- chlorocrotonic acid chlorideare added dropwise to this solution while stirring, the addition beingmade within hour and the pH of the mixture being kept at 6-7 by thesimultaneous dropwise addition of an aqueous solution of sodiumcarbonate. As soon as no more diazotisable amino groups can be tracedand, thus, the condensation reaction has finished, the dyestuif solutionis carefully evaporated to dryness in a vacuum at 40-50". The newdyestuff of the formula is obtained as a black powder which dissolvesvery easily in water with a violet-black colour.

Cotton is impregnated with a 20% dyestuff solution, which solution alsocontains 20 parts of sodium carbonate and 200 parts of urea per litre.The impregnated material is squeezed out, dried in a moderately warmstream of air and then heated for 4 minutes at 140-160". It is thensoaped at the boil in a 0.5% soap solution, rinsed with cold water anddried. A greenish grey dyeing which is last to light and wet isobtained.

Table 4 gives further metal-containing dyestufis according to theinvention which are produced by using equivalent amounts of heavymetal-containing aminoazo dyestuffs and acylating as described in theabove example.

EXAMPLE 5 31.9 parts of l-amino'8-hydroxynaphthalene-3.-disulphonic acidare dissolved with sodium carbonate at a pH value of 6-6.5, in 200 partsof water. 21 parts of [ichlorocrotonic acid chloride in 50 parts ofacetone are then added dropwise within 1 hour at 20-25 and the pH valueof the reaction solution is kept at 6-6.5 by the gradual additiondropwise of sodium carbonate solution. When no more diazotisable aminogroups can be traced, the reaction product is precipitated with sodiumchloride, filtered off and dissolved in 300 parts of water at 20-25. 30parts of sodium bicarbonate are added to this solution and then asolution of 17.3 parts of diazotised l-aminobenzene-Z-sulphonic acid ispoured in within 30 minutes. As soon as the coupling is complete, thenew dyestuif which precipitates of the formula IIOaS- BOITI is filteredoff, washed with diluted sodium chloride solution and dried in thevacuum at 40-45. It is a dark powder which dissolves in water with a redand in concentrated sulphuric acid with a blue-red colour.

If cotton is foularded at 20 with a 2% aqueous solution of thisdyestuff, dried, then treated with a 1% sodium hydroxide solution whichcontains 30% sodium chloride, steamed for 5 minutes at -1032 then rinsedand soaped at the boil for 30 minutes, a brilliant red dyeing which isfast to boiling is obtained.

If in the above example, instead of the condensation product from1-amino-8-hydroxynaphthaiene-3.6-disulphonic acid and fl-chlorocrotonicacid chloride, at corresponding amount of the coupling components givenin the Table 4 Metal complex compound oi No. Shade on Amino azo dystuflMetal to cotton dye ratio 1.G-nitro-Ldiazo-2-hydroxynaphthalenc-4-sulphonle acid-)2-amino-5-hydroxy-011:1 raisin.

na hthalene-Hui honic acid. 2. G-nitro-l-diazo-Z-hyoxynnphthaleneesulphonicacid 1-amino-8-hydrory- C022 reddish nnphthaleneksulphonlc acid. black. 3. 1-diazo-2-hydroxynophthalene-Qsulphonic acidl-uminoB-hydroxy- Cuzl bluish naphthalene-Hui honic acid. violet. 4.G-nitro-l-diezo-Z-hy oxynnphthalene+sulphonlc acid -el-omino-s-hydroxy-Cuzl reddish nnphthaiene-Ld-deulphonio acid. blue.

following Table is used, and if instead of I-aminobenzene-Z-sulphonicacid, a corresponding amount of the diazo components given in the tableis used and otherwise the same procedure is followed, then dyestutfshaving wherein Z; is --NHCOCH=C(CI)CH and is linked to phenylene, Y is amember selected from the group consisting similar properties areobtained. 5 i of hydroxyl and amino,

Table 5 No. Diazonium compound Coupling component Shade on cotton1-aminobenzeue-2-snlphonic acid1-(8chloroerotonylamino)-8-hydroxynaphred.

thaleno-4.6-disu1phonic acid. 1-amino4-lnethylbenzeno-2sulphonic neld dored. l-anzigioli-acetylaminobcnzene--sulphonic do red.

ac 1-aminobenzene-2-sulphonic acid2-(fl-chiorocrotonylamino)-8Phydroxynsphorange.

' thalene-G-sulphonic acid. l-slnmobenzene-2-sulphonie acid2-(fl-chlorocrotonylamino)-5-hydroxynaphorange.

thalene-I-suiphcnic acid. 1sn;gm-4-acotylarninobenzene-Z-sulphonic doorange.

ac 1-hydroxy-4-aminobenzene-2-carboxylic do orange.

acid-dsulphonic acid. i-aminobenzenc-z-sulphonic acid 1-(3it-chrocrotonylaminohenzoylamino)- red.

8-1113droxynnphthnlene-tm'disulphonic no 9.l-aminot-methylbenzene-2-sulphonic ncid...'..-.-do red. 10.l-nminobenzeneZ-sulphonic acid 1-(3-fi-chIorccrotonylnminobenzoylaminoyred.

8-lgdroxynaphthalene-tfi-disulphonic ac What we claim is:

1. Monoazo dyestufr' selected from the group consisting (a) compounds ofthe formula wherein Z vis a member selected from the group consisting Aris a member selected from the group consisting of phenyl, chlorophenyland naphthyl, and being substituted with one to two --SO H groups; (d)disulfopyrene-N=N-phenyl-Z dyestuif wherein Z is as aforedefined; (e)o,o'-dihydroxyphenyl-N=N-naphthyl dyestuir' with one Z group, asaforedefined, linked to the azo-free naphthyl ring;

(1') 0,0 dihydroxynaphthyl-N=N-naphthyl dyestufi having from 2 to 4 -SOH groups, not more than two of which are linked to each component of thesaid dyestuif, the naphthyl moiety being substitued with Z group, asaforedefined, at the azo-frce ring;

Z being in p-position to the azo group,

B is a member selected from the group consisting of hydrogen andhydroxy,

13., being a member selected from the group consisting of hydrogen andZ, not more than one of B B and B; being Z, and n is an integer of i to2;

(b) compounds of the formula wherein (g) compounds of the formula Z isas aforedefined; and

(h) copper, chromium and cobalt metal complex compounds of dyestuffsdefined in (e), H) and (g).

3. A dye of the formula 2. A dye of the formula Z 0H NH: BOIH N=N- 11 1so H (80815011 p my a Q OH NH-CQ-CH=G CH1 wherein OIH Z and n are 'asaforedefined; 4. A dye of the formula (0) compounds of the formula 801B:

01 g (HOsS):-Phenyl-N==N-C(|3CH; j CHNN Y- Hots N/ 0 01 N 7 l NH- 0-CH-GAr J H. CH:

5. A; dye of the formula 2,743,267 Heyna et a1 Apr. 24, 1956 2,906,747Wolfrum Sept. 29, 1959 HO=S 0-C1 1 0 2,978,289 Barker et a1. Apr. 4,1961 2,984,659 llly May 16, 1961 N=N CH1 5 FOREIGN PATENTS BOflI SOQH1,200,241 France June 29, 1959 References Cited in the file of thispatent OTHER REFERENCES UNHED STATES PATENTS 10 Frick et al.: TextileResearch Journal," vol. 97, pages 2,339,739 Blackshaw et a1 Jan. 18,1944 92-99, 1957.

2,657,205 Heyna et a1 Oct. 27, 1953 Wegmann: Textile-Praxis, October1958, page 1056.

1. MONOAZO DYESTUFF SELECTED FROM THE GROUP CONSISTING OF (A) COMPOUNDSOF THE FORMULA